Reaction of [Cr(CO)6] with 2-pyridylamidoxime (PAO) in THF under reduced pressure resulted in the formation of the tris derivative [Cr(PAO)3]. The corresponding reaction in the presence of bipyridine gave the binuclear complex [Cr2O4(PAO)(bpy)]. On the other hand, reaction of [Mo(CO)6] with 2-pyridylamidoxime in air resulted in the formation of [Mo2O6(PAO)2], while in the presence of bipyridine, the reaction gave two isomers with molecular formula [Mo(CO)4(PAO)].bpy, where bpy form hydrogen bonds to the coordinated 2-pyridylamidoxime. Reactions of [W(CO)6] with PAO ligand in air yielded the complex [W2O6(PAO)2]. The structures of all complexes were characterized by elemental analyses, IR, and 1H NMR spectroscopy. The thermal properties of the complexes were also studied.